Polymers of 5-(3-perfluoroalkyl-1,2,4-oxadiazolyl)olefins

ABSTRACT

MONEMERIC 5-(3 - PRFULOROALKYL-1,2,4-OXADIAZOLKYL)OLEFINS FORM HOMOPOLYMERS AND COPOLYMERS WITH OTHER ETHYLENICALLY UNSATURATED COMMONMERS. THE POLYMERS OBTAINED HAVE VALUABLE SOIL REPELLENT AND DYESITE PROPERTIES WHICH ARE ESPECIALLY USEFUL IN TEXTILE FINISHES. PREFERRED COMPOUNDS EXEMPLIFIED ARE 1,2-BIS(5-(3-N-PERFLUOROHEP TYL-1,2,4-OXADIAZOLYL) (ETHYLENE AND 5-ISOPROPPENYL-3-N-PERFLUROHEPTYL-1,2,4-OXADIAZOLE.

United States Patent Office 3,754,057 Patented Aug. 21, 1973 US. Cl.260-901 Claims ABSTRACT OF THE DISCLOSURE Monomeric -(3perfluoroalkyl-1,2,4-oxadiazolyl)olefins form homopolymers andcopolymers with other ethylenically unsaturated comonomers. The polymersobtained have valuable soil repellent and dyesite properties which areespecially useful in textile finishes. Preferred compounds exemplifiedare 1,2-bis[5-(3-n-perfiuorohepty1-1,2,4-oxadiazo1yl) ]ethylene and5-isopropenyl-3-n-perfluoroheptyl-1,2,4-oxadiazole.

This is a divisional of application Ser. No. 833,706, filed on June 16,1969, now US. Pat. No. 3,645,985.

THE INVENTION wherein m is an integer of 1 to 18, preferably 3 to 7 andmost preferably 7 and R is -CH=CH1 01' C=CHg A second type of monomercompounds are represented by the following formula:

N=C -R2 CmF2m+l wherein m is an integer of 1 to 18, preferably 3 to 7and most preferably 7; and

R is an ethylenically unsaturated hydrocarbon radical derived fromfumaric, maleic, citraconic, mesaconic or itaconic acid.

The corresponding polymers of the monomers of this invention are thosehaving skeletal chains comprising re-.

peating units of N (III) respectively, wherein m is as defined above,and R is CH:-CH: 01' CH-CH2-' R is a hydrocarbon radical derived fromfumaric, maleic,

citraconic, mesaconic or itaconic acid.

The invention related further to new compounds of the formula wherein mand R are as above defined which compounds are used as starting materialfor the monomers of the Formula H.

'As indicated in the foregoing formulae, perfluoro groups of 1 to 18carbon atoms may be employed and it is to be understood that mixtures ofcompounds of perfluoro groups of different numbers of carbon atomswithin the foreoing range can be employed. Both straight and branchedchain perfluoro groups are contemplated.

The monomer compounds of Formula I and Formula II may be prepared byprocedures well-known to those skilled in the art, for example, asdescribed in Brown and Wetzel Journ. of Org. Chem. 30, 3734 (1965). Inboth instances the fluorinated O-substituted amidoximes employed as astarting material may be prepared by known procedures such as describedin the copending application Ser. No. 586,956 according to the reactionoutlined in the following sequences:

For the monomers of Formula I NH, 0 .1 ll mF2m+1 =NO R1 HY For themonomers of Formula II NH, o o

2omrim+1-o o-m-o N-0H Y R and R as well as m are defined above and Y ishalogen such as chlorine or bromine. The condensation is effected merelyby bringing together the amidoxime and the acyl halide.

It is preferred to conduct the reaction in a solvent, suitably dryacetonitrile, and to stir the reaction mixture for from about 1 hour toabout 12 hours at a temperature of from about 25 C. to about C. toinsure highest yields. The product is recovered by evaporating thesolvent. The product, which remains as a residue, can be purified, ifdesired, by recrystallization from a hydrocarbon solvent, such aspetroleum ether mixed with a ketonem such as acetone, or an ester, suchas ethyl acetate.

The starting materials for the O-substituted amidoximes are readilyavailable or can be prepared by techniques within the capabilities ofthose skilled in the art. The preparation of perfiuoroacylamidoximes aredescribed in Brown and Wetzel in J. Org. Chem. 30, 3734 (1965).

The acyl halides are items of commerce or can be obtained by proceduresvery well known to those skilled in the art.

The monomer compounds of the Formulas I and 11 may be prepared byreacting O-acyl perfiuoroacylamidoximes with cycling agents or bythermal dehydration. Illustrative of the O-acyl perfluoroacylamidoximesuseful in the practice of the invention are O-methacrylylperfluorooctanamidoxime, O-methacrylyl 'acetamidoxime, O- fumarylbis-(n-perfluorooctanamidoxime) and O-fumarylbis-(n-perfluorobutyramidoxime) Representative cycling agents effectivein ring-closing the aforementioned O-acyl perfluoroacylamidoximes arephosphorous pentoxide, formamidine or s-triazine.

The thermal dehydration is effected by heating the amidoximes in adistilling flask with a direct flame under normal pressure or undervacuum.

The polymers contemplated by the present invention include homopolymersof the novel fluoromonomers, copolymers with other ethylenicallyunsaturated monomers, and physical blends of such homopolymers andcopolymers together and/ or with other polymers.

Since the novel homopolymers and copolymers find substantial use astextile finishes, it is often desirable to include in the monomermixture from about 0.2 to about 5% by weight of a reactive acrylic,which permits crosslinking either by heat or cross-linking agents. Suchreactive fluorocopolymers give textile finishes with superior resistanceto washing, dry cleaning, scrubbing, abrasion, and crocking, both wetand dry, and also a better durability of the oil and water repellencyproperties.

It is also advantageous, especially in the preparation of fabricfinishes, to use blends of emulsions or solutions of other polymers suchas polyalkyl acrylates and polyalkyl methacrylates, illustrative ofwhich is poly (n-octylmethacrylate). Such blends serve both tosubstantially reduce the amount of required fluorinated polymer toachieve commercially acceptable repellency characteristics and to imparta softer finish to the fabric than if the more brittle fluorinatedpolymers were used alone.

Polymerization of the monomers may be carried out in bulk, solution, oremulsion. The preferred polymerization techniques are emulsionpolymerization in an aqueous medium and solution polymerization. Thepolymerization temperature will vary depending upon the catalyst chosen.

In emulsion polymerization, the monomer or monomers to be polymerizedare emulsified preferably together with a solvent such as acetone in awater solution of a surface active agent to a given monomerconcentration of from about 5% to about 50% Usually the temperature israised to between 70-100 to effect polymerization in the presence of anadded catalyst. A suitable catalyst may be any one of the commonly knownwater soluble agents for initiating the polymerization of anethylenically unsaturated compound. The concentration of the catalystfor the polymerization is usually between 0.1% and 2% based upon theweight of the monomers.

Suitable surfactants or emulsifying agents include cationic, anionic ornon-ionic types. Since the cationic types can be used in most textiletreating baths, they are preferred. The hydrophobic portion of thesurfactant may be hydrocarbon or fluorinated hydrocarbon.

Suitable surfactants that may be used include, for example, non-ionicsurfactants in which the hydrophilic group is a poly(ethoxy) group andthe hydrophobic portion is either a hydrocarbon or a fluorocarbon groupsuch as the ethylene oxide condensates of alkyl phenols, alkanols,alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkyl carboxylicacids, fluoroalkyl amides and the like.

Suitable cationic surfactants include for example quaternary ammoniumsalts or amine salts containing at least one long chain alkyl,fluoroalkyl, or high alkyl substituted benzene or naphthalene group toprovide the hydrophobic portion.

Polymerization is preferably carried out for a reaction period adjustedto obtain essentially quantitative conversion of the fluorinatedmonomer. The optimum reaction time will depend upon the catalyst usedand the polymerization temperature and other conditions, but willgenerally be in the range of from 0.5 to 24 hours.

The polymerization is generally most conveniently and preferably carriedout at atmospheric pressure Wherever possible.

In solution polymerization, the monomer or monomers are dissolved in asuitable solvent such as fluorinated solvents, for example,fluorohalogenated hydrocarbons, hexafluoroxylene, trifluorotoluene ormixtures thereof with acetone and/or ethyl acetate, other fluorinatedsolvents and the like, and then polymerized in a reaction vessel usinginitiators such as azobisisobutyronitrile, benzoyl peroxide, or t-butylperbenzoate, at concentrations of 0.1 to 2.0% at 70-l40 C., undernitrogen.

As mentioned, besides homopolymers, valuable copolymers are obtained bypolymerization of the foregoing novel perfluorinated monomers with otherpolymerizable monomers having ethylene unsaturation.

Monomers of the type I show a copolymerization behavior similar toacrylate and methacrylate monomers. These comonomers are described indetail in C. E. Schildknecht, Vinyl and Related Polymers, pp. l75-255(John Wiley & Sons, Inc., New York 1952). Of these comonomers the mostpreferred are esters of acrylic and methacrylic acid with alkyl estergroups from 1 to 18 carbons such as methyl-, ethyl-, i-propyl-,n-butyl-, n-hexyl-, noctyl, 2-ethylhexyl-, n-dodecyl-, n-octadecylacrylate and methacrylate.

Monomers of type II show a copolymerization behavior similar tofumarates and maleates. Examples of suitable .comonomers for monomers oftype II are alkyl vinyl ethers, such as methyl vinyl ether, isopropylvinyl ether, isobutyl vinyl ether, 2-methoxyethyl vinyl ether, n-propylvinyl ether, t-butyl vinyl ether, isoamyl vinyl ether, nhexyl vinylether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether,i-methylheptyl vinyl ether, n-decyl vinyl ether, n-tetradecyl vinylether, and n-octadecyl vinyl ether.

Vinyl comonomers with short side chains are preferred.

Of these vinyl ethers, the most preferred ones are: methyl vinyl ether,ethyl vinyl ether, n-propylvinyl ether, isopropyl vinyl ether,Z-methoxyethyl vinyl ether and 2- chloroethyl vinyl ether.

Propylene, butylene and isobutylene are preferred aolefins useful ascomonomers with the novel fiuoro monomers of the present invention.Especially preferred is isobutylene. Straight and branched chaina-olefins are useful With up to 18 carbon atoms in the side chain.

Useful copolymers of the novel perfluorinated compounds of the inventionare formed with vinyl esters, e.g. vinyl acetate, vinyl esters ofsubstituted acids, such as for example, vinyl methoxyacetate, vinyltrimethylacetate, vinyl isobutyrate, isopropenyl butyrate, vinyllactate, vinyl caprylate, vinyl pelargonate, vinyl myristate, vinyloleate and vinyl linoleate; vinyl esters of aromatic acids, such asvinyl benzoate, and vinyl alkoxybenzoates.

lPreferred of the foregoing vinyl esters are vinyl acetate, vinylpropionate, vinyl benzoate, and isopropenyl acetate.

Also useful as comonomers are styrene and related monomers whichcopolymerize readily with the novel esters of this invention such asa-methylstyrene, p-methylstyrene, 3,4-dimethylstyrene,2,4,6-trimethylstyrene, methylstyrene, 2,5-diethylstyrene.

Additional useful comonomers are ethylene, and ch1oro-, fluoroandcyano-derivatives of ethylene such as vinyl chloride, vinylidenechloride, vinyl fluoride, vinylidene fluoride, acrylonitrile,methacrylonitrile, tetrafluoroethylene, trifluorochloroethylene,hexafluoropropylene; acrylate and methacrylate monomers, particularlythose with 1 to 18 carbon atoms in the esters groups such as n-propylmethacrylate, methyl methacrylate, t-butyl methacrylate,

n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate,butyl acrylate, octyl acrylate, tetradecyl acrylate, s-butyl acrylate,2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and phenyl acrylate;dienes particularly 1,3-butadiene, isoprene, and chloroprene,2-fluoro-butadiene, 1,1,3-trifluorobutadiene,1,l,2,3-tetrafluorobutadiene, 1,1,2-trifluoro-3,4-dichloro-butadiene,and tri and pentafluoro butadiene and isoprene; nitrogen-vinyl monomerssuch as vinyl pyridine, N-vinylimides, amides, and secondary cyclicamines, like vinyl succinimide, vinyl pyrrolidone, N-vinyl carbazole andthe like.

Also useful as comonomers with the novel monomers of the presentinvention are vinyl monomers which contain perfluorinated side chains.Examples of such perfluorinated monomers are vinyl ethers of the typedisclosed in U.S. 2,732,370 and U.S. 2,828,025; vinyl esters containingfluorinated alkyl groups disclosed in U.S. 2,592,069 and U.S. 2,436,144. Other useful monomers are acrylates and methacrylates andderivatives thereof such as those disclosed in U.S. 2,628,958; U.S.3,256,230; U.S. 2,839,513; U.S. 3,282,905; U.S. 3,252,932 and U.S.3,304,278.

As mentioned, it may also be desirable to include a minor amount ofother reactive comonomers in order to improve the wash and dry-cleanproperties of the novel textile finishes obtained according to thepractice of this invention. Such monomers act as cross-linking agentsduring the curing operation. Such reactive comonomers are generallyemployed in amounts of 0.1 to 2%. By way of illustration, reactivemonomers which may be included are: acrylic acid, methacrylic acid,acrylamide, methacrylamide, N-methylolacrylamide, Z-hydroxyethylmethacrylate or acrylate, hydroxypropyl acrylate or methacrylate, andt-butylaminoethyl methacrylate or glycidyl methylate. Of the foregoing,N-methylolacrylamide and 2-hydroxyethyl methacrylate are preferred.

Coatings of the homopolymers and copolymers according to the presentinvention can be prepared and applied from solvent solutions or fromaqueous emulsions. Suitable solvents are fluoroalkanes,fluorochloroalkanes, fluoroalkyl-substituted aromatics, alkyl esters ofperfluoroalkanoic acids, chlorinated alkanes or aromatics, hydrocarbonaromatics, ketones, esters, and ethers. Especially useful as solventsare the fluorinated liquids, and especially a,u,a-trifluorotoluene,otherwise known as benzotrifluoride, hexafluoroxylene and mixtures ofthese with ethyl acetate or acetone and the like. Concentrations of thefluorinated polymers of the present invention in solvents to providecoatings with eifective oil and water repellency properties willgenerally be of the order of 0.01 to and preferably from 0.1 to 2.0% byweight.

As indicated, blends of the emulsions of the polymers of this inventionwith blended emulsions of other polymers and copolymers are particularlyuseful in textile finishes.

Non-fluorinated polymers useful in such blends, include for example, butwithout limitation, polymers and copolymers of alkyl acrylates and alkylmethacrylates, such as methyl methacrylate, ethyl methacrylate, hexylmethacrylate, and n-octyl methacrylate. A particularly suitable polymeris poly (n-octyl methacrylate) Also useful are polymers and copolymersof acrylic acid, methacrylic acid, styrene, alkyl styrene, butadiene,2-methyl-l,3-butadiene, 2-chloro-l,3-butadiene; polymers and copolymersof vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate,vinyl stearate, vinyl 2-ethylhexanoate; polymers and copolymers of vinylhalides and vinylidene halides, such as vinyl chloride, vinylidenechloride, vinyl fluoride, vinylidene fluoride; polymers and copolymersof allyl esters such as allyl propionate, or allyl caprylate; polymersand copolymers of vinyl ketones, such as vinyl methyl ketone, vinylethyl ketone, and the like; polymers and copolymers of vinyl others suchas methyl vinyl ether, cetyl vinyl ether, and the like; polymers andcopolymers of acrylamide, methacrylamide, N- methylol acrylamide,N-methylol methacrylamide, N-isopropyl acrylamide, and acrylonitrile andmethacrylonitrile.

For example, from about 20 to 97% by weight of a homopolymer ofpoly(n-octyl methacrylate) blended with the polymers of this inventionprovides very useful coating compositions which retain surprisingly highrepellency ratings even though the relative amount of perfluorinatedpolymer of this invention is relatively low. Of course, it is understoodthat besides application to textiles, the coatings of the perfiuorinatedpolymers of the present invention are useful in providing oil and waterrepellent coatings for leather, paper, wood, masonry, metals, plastics,glass, painted surfaces, and the like. Coatings may be readily appliedby various coating techniques familiar to the art, such as dipping,spraying, brushing, padding, roll coating, and the like.

For evaluation purposes, the textile material in the following exampleswas dipped in the bath comprising the polymer to be evaluated and theamount of the retailed solution adjusted so as to leave approximately 2%of polymer by weight of the fabric on the fabric. The fabric is dried atroom temperature and then cured in an oven at a temperature of about C.for about 2 minutes.

The type of textile material which is coated is not critical. Forevaluation purposes, repellency ratings for cotton or wool aredetermined as a standard screening procedure; however, such fibers suchas fiberglass, silk, regenerated cellulose, cellulose esters and ethers,polyamides, polyesters, polyacrylonitrile, polyacrylates and otherfibers alone or blended or in combination may be coated with thepolymers of the present invention.

The present invention also relates to compositions comprising difficultdyeable organic materials and, as an assistant and dyesite, ahomopolymer of a compound of Formula I or II or copolymers thereof.While the inherent physical properties of synthetic organic polymericsubstances, such as poly-a-olefins of the polyethylene and polypropylenetype, make possible a wide range of applications, they also present anumber of problems in processing and use, such as a marked resistance todyeing. One embodiment of the present invention is based on thediscovery that the instant polymers, render diflicult dyeable organicmaterial more amenable to dyeing. Particularly effective for thispurpose are homoand copolymers of 5-isopropenyl-3-n-perfiuoroheptyl1,2,4 oxadiazole and trans-1,2-bis-[5-(3-perfluoroheptyl 1,2,4oxadiazolyD] ethylene.

The compounds of this invention may be incorporated in the difficultdyeable organic substance during the usual processing operations. Thusfor example, they can be introduced into polypropylene by hot milling,the polymers then being extruded, pressed, blow molded or the like, intofilms, fibers, filaments, hollow shapes and the like. The newcompositions can be dyed, either directly after compounding or afterfurther processing, such as the formation of yarns or fabrics.

The conditions of dyeing will of course vary with the particular dyeemployed. Generally the nature of the dye is not restricted and any ofthe many known acidic, direct and metallized dyes may be employed.Generally from about 0.05 to 10% and preferably about 0.1 to 6% byweight of the instant polymers in the difficult dyeable organicmaterial, is used, but the amount is not critical.

While polypropylene has been herein mentioned specifically, it isapparent that the instant compounds are useful in numerous othersubstances whose regular and inert chemical structures tend to resistdyes. Materials for which the compounds of the present invention areuseful thus include synthetic organic polymeric substances, bothhomopolymeric and copolymeric, such as vinyl resins, poly-a-olefins,polyurethanes, polyamides, polyesters, polycarbonates, polyacetals,polystyrene, polyacrylics, and the like.

In the examples below, the repellency ratings were determined asfollows:

The AATCC water spray test rating was determined according to StandardTest method 22-1966 of the American Association of Textile Chemists andColorists, XXXVII, 1961, p. 1952 (also designated ASTM-D 583- Oilrepellency is measured by the 3-M-Oi1 test procedure of Grajek andPeterson, Textile Research Journal, April 1962, p. 323.

The following examples describing certain representative embodiments ofthis invention will serve to further illustrate the nature of thisinvention. Unless otherwise specified, the relationship of parts byweight to parts by voltime is that of grams to cubic centimeters, andtemperatures are degrees centigrade.

EXAMPLE I S-isopropenyl-3-n-perfluoroheptyl-1,2,4-oxadiazole (A) Omethacrylyl perfluorooctanamidoxime.Perfluorooctanamidoxime (preparedaccording to H. C. Brown and C. R. Wetzel, J. Org. Chem. 30, 3734(1965); 27 g., 0.063 mole) is finely pulverized and suspended in dryacetonitrile (140 ml.). A solution of methacrylyl chloride (6.6 g.,0.063 mole) in 14 ml. of dry acetonitrile is added to the suspensiondropwise at room temperature with vigorous stirring. The mixture isstirred for two hours at room temperature and then refluxed for twoadditional hours. Removal of the solvent under reduced pressure leaves acrystalline product, which after crystallization from acetonehexaneaffords 27 g. (86%) of O-methacrylyl perfluorooctanamidoxime, M.P.1325-137.

The NMR spectrum (acetone-d shows a doublet at 2.006(CH two multipletsat 5.71 and 6.24 for the vinylic protons and a broad signal at 6.97 forthe NH The infrared spectrum has absorptions at 2.8-3.0;1. (NI-I2), 5.75(C=O), 6.0 (C=N) and 6.2 (C=C).

Analysis.-Calcd. for C F H N O (percent): C, 29.04; H, 1.42. Found(percent): C, 29.24; H, 1.36.

If in the above example instead of perfluorooctanamidoximeperfluorobutylamidoxime, perfluorododecanamidoxime orperfluorononadecanamidoxime and instead of methacrylyl chloride acrylylchloride are employed, there is obtained O-acrylylperfluorobutyramidoxime, O-acrylyl perfluorododecanamidoxime orO-acrylyl perfluorononadecanamidoxirne.

(B) isopropenyl 3 n perfluoroheptyl 1,2,4- oxadiazole.-O methacrylylperfiuorooctaneamidoxi'me (0.054 mole) is thoroughly mixed with anexcess of phosphorous pentoxide (0.35 mole) and placed in a distillingflask connected to an ice cooled trap. The flask is then heated with adirect flame under an initial vacuum of 1 mm. Hg of pressure. Thereaction is quick and once started, it proceeds without additionalheating. The yield of crude product is 7.0 grams, B.P. 63 at 0.09 mm. ofpressure.

The NMR spectrum shows a singlet at 1.86 for the methyl protons and twomultiplets at 5.3 and 5.9 for the vinyl protons.

If in the above example instead of O-methacrylylperfluorooctanamidoxime, O-acrylyl perfluorobutyramidoxime, O-acrylylperfluorododecanamidoxime or O-acrylyl perfluorononadecanamidoxime areemployed, 5-vinyl-3-nperfluoropropyl-1,2,4-oxadiazole, 5vinyl-3-n-perfluoroundecyl 1,2,4 oxadiazole or5-vinyl-3-n-perfluorooctadecyl-l,2,4-oxadiazole respectively areobtained.

EXAMPLE 2 Trans-1,2-bis [5-( 3-n-perfluoroheptyl-1,2,4-

oxadiazolyl) ethylene (A) O fumaryl bis (n-perfluorooctanamidoxime).-Fumaryl chloride (3.2 g. 0.0209 mole) in 2-0 ml. of spectrogradeacetonitrile is added dropwise to a stirred mixture ofn-perfluorooctanamidoxime (19 g., 0.044 mole) in ml. of acetonitrile.After the addition is completed, the reaction mixture is boiled gentlyfor ninety minutes While a stream of nitrogen is passed through thereaction flask to carry off the evolved hydrogen chloride. The productwas filtered and dried to afford 19.5 grams of O-fumarylbis(n-perfluorooctanamidoxime), M.P. 266 (dec.).

AnalySis.Calcd. for C2UHGF3ON404 (PI'Cent): C, 25.65; H, 0.64; F, 60.87;N, 5.98. Found (percent): C, 25.79; H, 0.60; F, 61.40; N, 5.85.

If in the above example instead of fumaryl chloride, citraconylchloride, mesaconyl chloride or itaconyl chloride are employed,O-fumaryl bis(n-perfluorooctanamidoxime), O-citraconyl, O-mesaconyl oritaconyl bis (n-perfluorooctanamidoxime) respectively are obtained.

(B) Trans 1,2 bis[5-(3 n perfluoroheptyl-l,2,4- oxadiazolyl)]ethylene.-O-fumaryl -bis (n-perfluorooctanamidoxime), (3.0 grams) isplaced in a round bottom flask and heated with direct flame until allmelts. The cooled reaction mixture is crystallized from chloroform toafford 2.3 grams of yellow product MP. 83-84". The ultraviloet spectrum(methanol) has absorption at A and A m with an extraction coeflicient of12600 and 13800 respectively.

Analysis.-Calcd. for C H F N O (percent): C, 26.88; H, 0.22; F, 63.31;N, 6.22. Found (percent): C, 26.99; H, 0.17; F, 63.27; N, 7.72.

If in the above example instead of O-fumarylbis(nperfluorooctanamidoxime), O-citraconyl, O-mesaconyl or O-itaconylbis(n-perfluorooctanamidoxime) are employed,

transl,2-bis[5-(3-n-perfluoroheptyl-1,2,4-oxadiazolyl) ethylene,

cisand trans-1,2-bis[5-(3-n-perfiuoroheptyl-l,2,4-

oxadiazolyl) ]prepene, and

2,3-bis [5- 3-n-perfluoroheptyl-1,2,4-oxadiazolyl) propene respectivelyare obtained.

EXAMPLE 3 Trans-1,2-bis[5-(3-n-perfluoropropyl-1,2,4- oxadiazolyl)ethylene (A) O-fumaryl bis(n-perfluorobutyramidoxime.This compound isprepared from fumaryl chloride and n-perfluorobutyramidoxime followingan analogous procedure as Part A of Example 2. The yield was 87% and theproduct melts at 277 with decompositions.

Analysis.Ca1cd. for C H F N Q, (percent): C, 26.87; H, 1.12; F, 49.60;N, 10.44. Found (perc nt): C, 27.00; H, 1.12; F, 49.55; N, 10.53.

If in the above example instead of n-perfluorobutyramidoxime,n-perfluorododecanamidoxime or n-perfluorononadecanamidoxime areemployed, O-fumaryl bis (n-perfluorobutyramidoxime), O-fumarylbis(n-perfluorododecanamidoxime) or O-fumarylbis(n-perfluorononadecanamidoxime) respectively are obtained.

(B) Trans-1,2-bis[5- 3-n-perfluoropropyl-1,2,4-oxadiazolyl)]ethylene.--The dehydration of 0-fumaryl bis(nperfluorobutyramidoxime) ofA was carried out as described in Part B of Example 2. The product iscrystal lized from petroleum ether, M.P. 62-65.

If in the above example instead of O-fumarylbis(n-perfluorobutyramidoxime), O-fumarylbis(n-perfluorododecanamidoxime) or O-fumarylbis(n-perfluorononadecanamidoxime) are employed,

trans-1,2,-bis (5-(3-n-perfiuoropropyl-1,2,4-oxadiazolyl) ethylene,

H. C. Brown and C. R. Wetzel, J. Org. Chem.,30, 3734 (1965).

9 trans-1,2-bis (3-n-perfluoroundecyl-1,2,4-oxadiazolyl) ethylene orTABLE II trans-1,2-bis[5-(3-n-perfluorooctadecyl-1,2,4- Composition ofblend oxad1azolyl)] ethylene qgggil g g Poly (m 11 respectively areobtained. 5 5,25,52, 5; 22%;; my (2% polymer fabric) (percent by(pereentby AATCC- EXAMPLE 4 Ex. weight weight) Fabric 3-M-Ol1 water 100parts of a mixture of 5-isopropenyl-3-n-perfluorom 100 33 33heptyl-l,2,4-oxadiazole prepared according to Example 1, 10 60 33 3g andn-octyl methacrylate as indicated in the following 50 40 so 80 Table Iand 1 part of azobisisobutyronitrile are sealed in 2% $3 an ampul undernitrogen and polymerized at 80 for 16 20 80 70 hours. Then the polymeris dissolved in 500 parts of benzo- 58",; 10 5 3g trifluoride andprecipitated into 20 times the amount of 5f 5 60 70 methanol. Thehomoand copolymers are obtained after high vacuum drying as fine, whitepowders. The copolymer composition, determined by fluorine analysis andthe If m the above example Instead of P Y repellency ratings obtainedwhen evaluated after applying ylate) y -P py tel'polymersbutflldlene-sty' 2% by weight of the novel polymers on f b i f a renecopolymers are employed, blends are obtained showbenzotrifluoridesolution, are given in the following table. mg enhanced repellancyTatlngs- TABLE I EXAMPLE 6 S-isopropenyl- 100 parts of a mixture ofequimolar amounts of transgggfi g; gggh (2% ggfg gfi 1,2bis[5-(3,n-perfluoroheptyl-1,2,4-oxadiazolyl)] ethyloxadiarole AA CC eneprepared according to Example 2, and a vinyl ether as 2232 353332 223?Fame E listed in the following Table III, 400 parts of ethyl acetate 0tt 90 90 and 1 part of azobisisobutyronitrile are sealed in an ampul4a.--- 100 None 1 -5 j so 80 under nitrogen and polymerized at 80 for 16hours. The 4b"; 5 g3 g8 resulting copolymer which precipitated duringthe polym- 4 78 8 70 80 erization reaction is then dissolved in 900parts of hexa- Z3 gg fluoroxylene and the polymer solution isprecipitated into 60 90 20 times the amount of methanol. Theprecipitated and dried polymers, white to slightly yellow powders ortacky materials are obtained in yields exceeding 80%.

If m the above example Instead of The copolymers are applied to fabricsfrom a 2% solu- 5-isopropenyl-3-n-perfluoroheptyl-1,2,4-oxadiazole, tionin hexafluoroxylene to provide a coating of 2% by5-vinyl-3-n-perfluoropropyl-1,2,4-oxadiazole, weight polymer on thefabric. The repellency ratings are5-vinyl-3-n-perfluoroundecyl-1,2,4-oxadiazole or determined as describedabove and are listed in the follow-5-vinyl-3-n-perfluorooctadecyl-1,2,4-oxadiazole ing Table IH.

TABLE III Repelleney (2% polymer on fabric) Example Vinyl etherAppearance of copolymer Fabric 1:: CH|=CHOCH3 Yellow-whitepowder-;::;-;;:;;.;.;..;.{ 6b.-..-. CHs=CHOC1Hs Yellow-white tackypolymer.-.-..'. 6C CHr=CHOCHaCH(CH;)g Yellow tacky polymer....-:.-:: 06d. CHa=GHOCH3CHgOCHa Yellow-tacky polymer.-...::;:;..;;;...{66---..:----:.': CH2=CHOCH1GF3 Yellow powderand instead of n-octylmethacrylate, 2-ethylhexyl acrylate If in the above example instead ofare employed, homoand copolymers are obtained showing improvedrepellency ratings.tIaniI-IfZ-bis[5-(3-n-perfluoroheptyl-1,2,4-oxad1azolyl)1 et y ene,EXAMPLE 5 cisor trans-l,2-bis[5-(3-n-perfluoroheptyl-l,2,4-

2% solutions of the homopolymer of S-isopropenyl-S-n- 70 oxadiazolyl)]propene or perfluoroheptyl-l,2,4-oxadiazole and poly(n-octylmethac-2,3-bis[5-(3-n-perfluoroheptyl-1,2,4-oxadiazolyl)] rylate) are blendedin various ratios as shown in the propene following table and the blendsapplied to fabrics as in the foregoing examples and the repellencyratings determined and instead of a vinyl ether styrene are employed,copolywith the results indicated in Table H. mers are obtained showingenhanced repellency ratings.

1 1 EXAMPLE 7 100 parts of a mixture of equimolar amounts of trans- 1,2bis[-(3-n-perfluoropropyl-1,2,4-oxadiazolyl)]ethylene produced accordingto Example 3, and methyl vinyl ether, 300 parts of ethyl acetate and 1part of azobisisobutyrom'trile are sealed in an ampul under nitrogen andpolymerized at 70 for 16 hours. After the polymerization the polymersolution is diluted with 600 parts of ethyl acetate and precipitatedinto times the amount of methanol. After drying, the copolymer isobtained as a fine, yellowish-white powder with melting point 93-102".

The critical free surface energy of a polymer film determined by contactangle measurements as described in, Advances in Chemistry, Series 43,pp. 1-49, A.C.S. (1964), is 12 dynes/cm. Copolymers having critical freesurface energies below 12 dynes/cm. can be obtained if in the aboveexample trans-1,2-bis[5-(3-n-perlluoropropan-1,2,4-oxadiazolyl)]ethylene is replaced by trans-1,2-bis[5- (3 nperfluoroundecan-1,2,4-oxadiazolyl)]ethylene or trans1,2-bis{5-(3-n-perfluorooctadecan-1,2,4-diazolyl)] ethylene.

What is claimed is:

1. A composition of matter comprising a blend of a polymer having askeletal chain comprising repeating units of N=C 1 CnLEzm-| -1 6 lwherein m is an integer of 1 to 18 and R is CHz-CH 01 -CH-CH:-

H3 and poly (alkyl methacrylate).

2. A composition of matter comprising a blend of a polymer having askeletal chain comprising repeating units of \N/ZJZ m is an integer of 1to 18 and R is an ethylene radical derived from fumaric, maleic,

citraconic, mesaconic, or itaconic acid wherein 5. Fabric coated with acopolymer having a skeletal chain comprising repeating units of whereinm is an integer of 1 to 18 and R is -CH1CHr- 01 -CH-CH;-

a so as to be rendered both water and oil repellent thereby.

6. Fabric coated with a copolymer having a skeletal chain comprisingrepeating units of N=o iw emawa &

wherein m is an integer of 1 to 18 and R is an ethylene radical derivedfrom fumaric, maleic,

citraconic, or itaconic acid so as to be rendered both water and oilrepellent thereby.

7. A composition comprising a diificult dyeable synthetic organicpolymeric substance and as an assistant and dyesite aperfluoroalkyl-oxadiazolyl olefinic polymer as set forth in claim 1.

8. A composition comprising a difficult dyeable synthetic organicpolymeric substance and as an assistant and dyesite aperfluoroalkyl-oxadiazolyl olefinic polymer as set forth in claim 2.

9. A composition comprising a difiicult dyeable synthetic organicpolymeric substance and as an assistant and dyesite aperfluoroalkyl-oxadiazolyl olefinic polymer as set forth in claim 5.

10. A composition comprising a difficult dyeable synthetic organicpolymeric substance and as an assistant and dyesite aperfluoroalkyl-oxadiazolyl olefinic polymer as set forth in claim 6.

References Cited UNITED STATES PATENTS 3,483,277 12/1969 Kleiner 260-897JOSEPH L. SCHOFER, Primary Examiner I. KIGHT III, Assistant Examiner US.Cl. X.R.

117-132 CF, 138.5, 138.8 UF, 1395A, A, 142, 145, 148 UA, 161 UN, 'UC;260-78.4 R, E, 78.5 B, 86.1 N, 89.5, 89.7, 874, 887, 890, 896, 897C,898, 899, 900

